JPH10130370A - Epoxy resin composition and semiconductor sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful as a semiconductor sealing material excellent in flame retardance and solder crack resistance due to development of excellent flame-retardance and possession of both moisture resistance and fluidity, by using a specific halogenated epoxy resin. SOLUTION: This composition comprises (A) a halogenated epoxy resin containing >=35wt.% of a binuclear substance component obtained by reaction (i) a compound which is a polyaddition reaction product (preferably one between dicyclopentadiene and phenol) between an unsaturated aliphatic cyclic hydrocarbon compound and a phenol and contains a halogen (preferably bromine) in its molecular structure with (ii) an epihalohydrin (preferably epichlorohydrin) and (B) a curing agent (preferably phenol novolak resin) as essential components. Preferably, the component A has <=25 poise melt viscosity at 150 deg.C, 15-50wt.% halogen content and 350-500g/eq epoxy equivalent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a novel, especially fluid,
It has an excellent balance of curability, heat resistance, and water resistance, and also has excellent flame retardancy, so it can be used for semiconductor encapsulation materials, laminated parts materials, electrical insulation materials, fiber reinforced composite materials, coating materials, molding materials, and adhesives. The present invention relates to an epoxy resin composition which is extremely useful for materials and the like, and a semiconductor encapsulant which is excellent in solder crack resistance during surface mounting in addition to those properties.

[0002]

2. Description of the Related Art Epoxy resins are generally cured with various curing agents to give cured products having excellent mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties. It is used in a wide range of fields, such as paints, laminates, molding materials, and casting materials. Flame-retardant epoxy resins are used for imparting flame retardancy to cured products.

In recent years, particularly in the application of semiconductor sealing materials, the mounting method has been rapidly shifting from the conventional pin insertion method to the surface mounting method, and a semiconductor sealing material having excellent solder crack resistance has been demanded. Have been. Further, semiconductor packages tend to be thinner in order to cope with higher packaging densities, and TSOP type packages having a thickness of 1 mm or less have come to be used. Therefore, in order to cope with these, in addition to solder crack resistance, a material having low melt viscosity and high fluidity is also required.

Conventionally, flame-retardant epoxy resins for use in semiconductor encapsulating materials meeting such required performances are disclosed, for example, in JP-A-61-171728 and JP-A-61-21.
No. 1333 discloses a technique in which a brominated dicyclopentadiene type epoxy resin is used as a flame retardant and partially mixed with another non-halogenated epoxy resin.

[0005]

However, the above-mentioned Japanese Patent Application Laid-Open No. Sho 61-1
In the technology using a brominated dicyclopentadiene type epoxy resin described in JP-A-71728 and JP-A-61-211333, although the moisture absorption rate is low, as can be seen from the GPC chart described in the examples, dinuclear dinuclear dicyclopentadiene type epoxy resin is used. Since the body component content is as low as about 12% by weight, the fluidity is poor and the moldability is poor. In addition, the compounding ratio of the inorganic filler could not be increased due to the poor fluidity. There was a problem that a product excellent in solder crack resistance during surface mounting could not be obtained.

An object of the present invention is to provide an epoxy resin composition exhibiting excellent flame retardancy and having both excellent moisture resistance and fluidity, as well as excellent flame retardancy and solder crack resistance. Is to provide a good semiconductor sealing material.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a halogenated epoxy resin is a polyaddition product of an unsaturated aliphatic cyclic hydrocarbon compound and a phenol, and has a molecular structure A reactant of a compound having a halogen atom with epihalohydrin, and 2
It has been found that the above-mentioned problems can be solved by using a core component content of 35% by weight or more, and the present invention has been completed.

That is, the present invention relates to a polyaddition reaction product of an unsaturated aliphatic cyclic hydrocarbon compound and a phenol, which is a reaction product of a compound having a halogen atom in its molecular structure with epihalohydrin, and An epoxy resin composition comprising, as essential components, a halogenated epoxy resin (A) having a binuclear component content of 35% by weight or more and a curing agent (B), and an unsaturated fat. A compound having a halogen atom in its molecular structure, which is a polyaddition reaction product of an aromatic hydrocarbon compound and a phenol;
A halogenated epoxy resin (A) which is a reaction product with epihalohydrin and has a binuclear component content of 35% by weight or more, a curing agent (B), and an inorganic filler (D) are essential components. The present invention relates to a semiconductor sealing material.

As described above, the halogenated epoxy resin (A) used in the present invention is a polyaddition product of an unsaturated aliphatic cyclic hydrocarbon compound and a phenol, and has a halogen atom in its molecular structure. It is a reaction product of a compound and epihalohydrin and has a binuclear component content of 35% by weight or more.

Since the halogenated epoxy resin (A) used in the present invention has such a molecular structure, it can provide a cured product having a low moisture absorption, a high adhesion, and a low elasticity in a solder bath temperature range. . In addition, dielectric constant and dielectric loss tangent are low,
When used as a semiconductor encapsulating material, a high computation speed can be imparted to a semiconductor. Furthermore, since the content of the binuclear component is within a suitable range, excellent fluidity can be exhibited at a low molecular weight.

Therefore, the semiconductor encapsulating material using this is TS
It can be applied to the molding of thin packages such as OP. Further, since the melt viscosity is low, it is possible to increase the blending amount of the inorganic filler, thereby realizing a reduction in the moisture absorption rate and the linear expansion coefficient of the package material. Therefore, a semiconductor molded with a semiconductor encapsulating material using this has excellent solder crack resistance during surface mounting.

The unsaturated alicyclic compound used in the halogenated epoxy resin (A) is preferably an aliphatic cyclic hydrocarbon compound having two or more unsaturated double bonds in one molecule. Although not limited, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorbon-2-ene, α-
Pinene, β-pinene, limonene and the like. Among these, dicyclopentadiene is preferred from the viewpoint of the property balance, particularly the heat resistance and the hygroscopicity. Further, since dicyclopentadiene is contained in the petroleum fraction, industrial aliphatic dicyclopentadiene may contain other aliphatic or aromatic dienes as impurities, but heat resistance, curability, In consideration of moldability and the like, it is desirable to use a product having a purity of 90% by weight or more of dicyclopentadiene.

Examples of the phenol include, but are not particularly limited to, phenol and substituted phenols to which an alkyl group, an alkenyl group, an allyl group, an aryl group, an aralkyl group or a halogen group is bonded. To be specific, cresol, xylenol,
Ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol,
Chlorphenol, bromophenol (o, m, p
-Isomer), bisphenol A, naphthol, dihydroxynaphthalene, and the like, but are not limited thereto. Also, a mixture of these may be used. Among these, phenol and cresol are particularly preferred from the viewpoint of excellent fluidity and curability.

Therefore, the polyaddition product of the unsaturated aliphatic cyclic hydrocarbon compound and the phenol is preferably a polyaddition product of dicyclopentadiene and phenol.

The halogen atom in the molecular structure of the polyaddition product is not particularly limited, but may be chlorine, bromine,
Fluorine, iodine and the like can be mentioned. Among them, a bromine atom is particularly preferable in view of excellent flame retardancy. The substitution position is not particularly limited, but from the viewpoint of excellent thermal decomposability, it is preferable that the ratio of substitution to the aromatic ring to which the glycidyl ether group is bonded is high. Conversely, halogen atoms substituted with an aliphatic cyclic hydrocarbon group are inferior in thermal decomposability, so that substitution with an aliphatic cyclic hydrocarbon group is preferably minimized.

As the epihalohydrin to be reacted with the above-mentioned compound, epichlorohydrin is the most common, and other examples include epiiodohydrin, epibromhydrin, β-methylepichlorohydrin, and the like.
Epichlorohydrin is preferred.

Further, the binuclear compound referred to in the halogenated epoxy resin (A) is a diglycidyl of a bisphenol compound having a binding group of an alicyclic compound in a reaction product of an unsaturated alicyclic compound and a phenol. Refers to ether products. This content is determined by gel permeation chromatography (GP
In the present invention, by setting the content of the binuclear component to 35% by weight or more, the above-described various performances can be exhibited. In particular, the binuclear component content is 35 to 9
It is preferable that the content is 0% by weight because heat resistance is remarkably improved in addition to fluidity.

The halogenated epoxy resin (A) contains 150
It is preferable that the melt viscosity at 25 ° C. is 25 poise or less from the viewpoint of fluidity. For the same reason, it is preferable that the epoxy equivalent is in the range of 350 to 500 g / eq.

The halogen content in the halogenated epoxy resin (A) can be appropriately selected according to the purpose. Specifically, 5 to 40% by weight of the organic component in the composition or semiconductor material is used. It is preferably within the range.

In particular, when the halogenated epoxy resin (A) is used in combination with another epoxy resin (C) described later, the halogen content in the halogenated epoxy resin (A) is in the range of 15 to 50% by weight. It is preferred that

Accordingly, a polyaddition product of dicyclopentadiene and phenol, which is a reaction product of a compound having a bromine atom in its molecular structure and epichlorohydrin, and whose binucleate component content is 35% by weight or more of a halogenated epoxy resin, and 150 ° C.
Has a melt viscosity of 25 poise or less and a halogen content of 15 poise.
It is preferably in the range of ５０50% by weight.

In order to obtain the halogenated epoxy resin (A) described in detail above, the production method is not particularly limited. For example, polyaddition of the above-mentioned phenols with the unsaturated aliphatic cyclic hydrocarbon compound A method (1) of halogenating the polyphenols obtained by the reaction and reacting them with epihalohydrin, or a polyaddition reaction of a phenol having a substituent with a halogen atom and an unsaturated aliphatic cyclic hydrocarbon compound, A method (2) of reacting epihalohydrin and a method (3) of halogenating a reaction product of epihalohydrin with a polyaddition reaction of a phenol and an unsaturated aliphatic cyclic hydrocarbon compound are exemplified. Among these production methods, production method (1) is preferable because the desired bromine content is easily obtained.

The method for producing the polyphenols which are intermediates in the production method (1) is not particularly limited, but in order to obtain a desired binuclear component content, the phenols and the phenols at the time of the reaction are required. It is preferable to adjust the molar ratio of the unsaturated aliphatic cyclic hydrocarbon compound, and it is preferable to use 2.5 mol or more of phenols per 1 mol of the unsaturated aliphatic cyclic hydrocarbon compound. Phenols /
Unsaturated aliphatic cyclic hydrocarbon compound = 4/1 to 15/1
When the synthesis is performed within the range of (molar ratio), an intermediate polyphenol resin which is preferable for obtaining the above-mentioned halogenated epoxy resin (A) is obtained. The method for producing the polyadduct is described in more detail below. A polyaddition catalyst is added to a molten or dissolved phenol, and an unsaturated aliphatic cyclic hydrocarbon compound is appropriately added thereto. The reaction is allowed to proceed, after which excess phenols are recovered by distillation to obtain a polyaddition reaction product. Here, as the polyaddition catalyst, an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as p-toluenesulfonic acid, or Al
Lewis acids such as Cl3 and BF3.

Next, by substituting the polyphenols obtained by such a polyaddition reaction with a halogen atom, the desired halogenated polyphenols which are intermediates of the halogenated epoxy resin (A) can be obtained. This halogen atom substitution reaction may be performed according to a known method. For example, a polyphenol is dissolved in an appropriate organic solvent, and an appropriate amount of bromine is added dropwise thereto. The amount of bromine at that time may be an amount corresponding to the total equivalent of the vacant ortho and para positions of the aromatic ring of the polyphenol. Thereafter, stirring is continued, and then the by-produced hydrogen bromide is neutralized with an alkali. After the neutralization, the reaction solution is dropped into a large amount of stirred water, reprecipitated, and then dried to obtain a target halogenated polyphenol.

Next, in order to obtain the halogenated epoxy resin (A), it is preferable to increase the glycidylation rate by 2 to 15 equivalents to the hydroxyl groups of the obtained halogenated polyphenols to reduce the melt viscosity. Add 3 to 10 equivalents of epihalohydrin and dissolve, then add 10 to 50% of 0.8 to 1.2 equivalents to the hydroxyl groups in the polyaddition reaction.
NaOH aqueous solution is required at a temperature of 50-80 ° C. for 3-5 hours. After the lowering, the stirring is continued at that temperature for about 0.5 to 2 hours. After standing, the lower saline solution is discarded. Subsequently, the excess epihalohydrin is recovered by distillation to obtain a crude resin. To this, an organic solvent such as toluene or MIBK is added, and the desired resin can be obtained through a water washing-dehydration-filtration-desolvation step. In addition, a solvent such as dioxane or DMSO may be used in the reaction for the purpose of reducing the amount of impurity chlorine.

The halogenated epoxy resin (A) described in detail above can be used alone in the epoxy resin composition or the semiconductor encapsulating material of the present invention. It is preferable to mix and use an appropriate amount.

As the other epoxy resin (C) used here, any known and commonly used epoxy resin can be used, for example, bisphenol A diglycidyl ether type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, Bisphenol A
Novolak type epoxy resin, bisphenol F novolak type epoxy resin, brominated phenol novolak type epoxy resin, tetrabromobisphenol A type epoxy resin, naphthol novolak type epoxy resin, biphenyl type bifunctional epoxy resin, dicyclopentadiene-phenol polyadduct type Epoxy resin, terpene-polyaddition type epoxy resin of unsaturated aliphatic cyclic hydrocarbon compound such as phenol polyaddition type epoxy resin and phenols, naphthalenediglycidyl ether type epoxy resin, hydroquinone diglycidyl ether type epoxy resin, Resorcin diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, fluorene bisphenol A diglycidyl ether type epoxy resin, tetraphenylene Ruetan type epoxy resins, naphthalene - and cresol co-condensed novolac type epoxy resins, - phenol co-condensed novolak type epoxy resin, naphthol
Examples include, but are not limited to, a condensation reaction type epoxy resin obtained by condensing a phenol or alkylphenol with a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and xylylene glycol. Further, a plurality of types of epoxy resins may be used in combination. Among these, orthocresol novolak type epoxy resin is particularly excellent in heat resistance and curability, and dicyclopentadiene-phenol polyaddition type epoxy resin is excellent in fluidity, hygroscopicity, adhesion, and electrical properties. A biphenyl-type bifunctional epoxy resin is preferred from the viewpoint of excellent fluidity and moldability.

The compounding ratio of the halogenated epoxy resin (A) and the other epoxy resin (C) is such that the melt viscosity at 150 ° C. becomes 3.0 poise or less, or A compounding ratio in which the halogen atom content in the total compounding amount is in the range of 3 to 25% by weight is preferable from the viewpoint of excellent balance between flame retardancy, fluidity, moldability, moisture resistance reliability, and physical properties of the cured product.

Next, as the curing agent (B) used as an essential component in the present invention, all compounds commonly used as curing agents for epoxy resins can be used, and are not particularly limited. However, for example, phenol novolak resin, orthocresol novolak resin, bisphenol A novolak resin, bisphenol F novolak resin, phenols-dicyclopentadiene polyaddition type resin, dihydroxynaphthalene novolak resin, polyhydric phenols having a xylidene group as a binding group Phenol-aralkyl resins, naphthol resins aliphatic amines such as diethylenetriamine and triethylenetetramine, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone, polyamide resins and Modified products thereof, acid anhydride-based curing agents such as maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride; latent curing agents such as dicyandiamide, imidazole, BF3-amine complex, and guanidine derivatives. Is mentioned. Above all, for semiconductor encapsulation materials, aromatic hydrocarbon-formaldehyde resins such as the above-mentioned phenol novolak resins have excellent curability, moldability and heat resistance, and phenol-aralkyl resins have curability, moldability and low water absorption. It is preferable because it is excellent.

The amount of the curing agent (C) used is not particularly limited as long as it can cure the epoxy resin, but is preferably not limited to the number of epoxy groups contained in one molecule of the epoxy resin used. The amount is such that the number of active hydrogens in the curing agent is close to the equivalent.

When each of the above compounds is used as a curing agent, a curing accelerator can be appropriately used.

As the curing accelerator, any known and commonly used curing accelerators can be used. Examples thereof include phosphorus compounds, tertiary amines, imidazoles, metal salts of organic acids, Lewis acids, and amine complex salts. Not only one kind but also two or more kinds can be used in combination.

In the epoxy resin composition of the present invention,
Further, the use of the inorganic filler (D) not only enhances the mechanical strength and hardness of the cured product, but also achieves a low water absorption and a low coefficient of linear expansion, and can enhance solder crack resistance. preferable.

The compounding amount is not particularly limited, but when it is used in the range of 70 to 95% by weight in the composition, the characteristics thereof are particularly remarkable, and in particular, the use of a solder-resistant material in a semiconductor sealing material application. It is preferable because the cracking property is very excellent.

It should be noted that the addition of an inorganic filler in an amount of 80% by weight or more in the present invention does not impair fluidity and moldability at all.

Examples of such an inorganic filler (D) include, but are not particularly limited to, fused silica, crystalline silica, alumina, talc, clay, glass fiber and the like. Among these, fused silica, especially in semiconductor encapsulating material applications,
Crystalline silica is generally used, and spherical silica is particularly preferred because of its excellent fluidity.

Further, in the composition of the present invention, various known and commonly used additive components such as a coloring agent, a flame retardant, a release agent, and a coupling agent can be appropriately compounded, if necessary.

In order to prepare a molding material from the above components, an epoxy resin, a curing agent, a curing accelerator, and other additives are sufficiently and uniformly mixed by a mixer or the like, and further mixed with a hot roll or a kneader. It can be obtained by melt-kneading, pulverizing after injection or cooling.

The thus obtained epoxy resin composition of the present invention is not particularly limited in its use.
For example, a semiconductor sealing material, a printed wiring board, an insulating powder coating material, a casting resin, a coating material, and the like can be given. Among these applications, semiconductor encapsulant applications are extremely useful because of their advantages such as remarkably excellent moldability and solder crack resistance. Hereinafter, the semiconductor sealing material of the present invention will be described in detail.

In recent years, semiconductor encapsulating materials have required characteristics such as excellent fluidity during molding when encapsulating a semiconductor and defects such as misalignment movement of a lead frame when encapsulating a chip having a fine structure. Moldability that does not occur, and excellent curability with smooth release from the mold are given.
Furthermore, the heat resistance after curing is excellent, the reliability of the semiconductor device is excellent, the water absorption is low, and the elastic modulus near the solder reflow temperature is low, so that the solder crack resistance when mounting on a printed circuit board There is a demand for a semiconductor encapsulating material that is extremely excellent.

In each of the above components, the semiconductor encapsulating material of the present invention contains the halogenated epoxy resin (A), the curing agent (B) and the inorganic filler (D) as essential components. In the present invention, it is preferable to use this as a flame retardant by further mixing it with another epoxy resin (C) in an appropriate amount.

The semiconductor encapsulating material of the present invention includes, in addition to the components of the epoxy resin composition described above, a flame retardant such as antimony trioxide and hexabromobenzene, a coloring agent such as carbon black and red iron oxide, and a natural wax. Various additives such as a release agent such as synthetic wax and a low-stress additive such as silicone oil, synthetic rubber and silicone rubber may be appropriately compounded.

In order to prepare a molding material using the semiconductor encapsulating material of the present invention, the above-mentioned components are sufficiently and uniformly mixed by a mixer or the like, and then melted and kneaded by a hot roll or a kneader, and then injected or After cooling, it can be obtained by crushing and tableting.

[0044]

Next, the present invention will be described in detail with reference to Production Examples, Examples and Comparative Examples. In the examples, all parts are by weight unless otherwise specified.

The melt viscosity is 50 Hz.
eseach equipment LTD. "ICI"
CONE & PLATE VISCOMETER ". The content of the binuclear component is determined by a gel permeation chromatography (GP) manufactured by Tosoh Corporation.
C) "(measurement conditions: flow rate = 1.0 ml / min, pressure = 92)
Kg / cm ² , column = G4, ³ , ² , 2HXL, detector = RI 32 × 10 ⁻⁶ RIUFS). The softening point is "Softening Point Measuring Device" (Heating: H
U-MK, detector ASP-M2) measured.

Production Example 1 Phenol 1128 was placed in a four-necked flask with a stirrer, thermometer and thermometer.
g, BF3.phenol complex 20g was added and mixed well. Thereafter, 198 g of dicyclopentadiene was added over 2 hours while maintaining the system temperature at 110 to 120 ° C. Thereafter, the temperature in the system was maintained at 120 ° C., and the mixture was heated and stirred for 6 hours. The magnesium compound “KW
After adding 45 g of "-1000" (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) and stirring for 20 minutes to deactivate the catalyst, the reaction solution was filtered. Excess phenol was distilled and recovered from the obtained transparent solution to obtain 394 g of an intermediate polyphenol resin. The softening point of this resin is 94 ° C, and the hydroxyl equivalent is 170 g /
eq.

340 g of this intermediate polyphenol resin is dissolved in 500 g of methanol, and
At ｇ15 ° C., 315 g of bromine was added dropwise over 4 hours. After completion of the dropwise addition, stirring was continued for 4 hours, and then 30% caustic soda was added dropwise to neutralize by-produced hydrogen bromide. After neutralization,
The reaction solution was added dropwise to 10 liters of water with vigorous stirring. The reprecipitated resin was dried to obtain 551 g of a brominated polyphenol resin.

480 g of epichlorohydrin is added to 480 g of the brominated polyphenol resin and dissolved. And 6
At 0 ° C., 135 g of 49% NaOH was added dropwise with stirring over 8 hours, and stirring was further continued for 30 minutes, after which 200 g of water was added and allowed to stand. The saline solution in the lower layer was discarded, and epichlorohydrin was recovered by distillation.
750 g, n-butanol 200 g and 30% NaOH2
After adding 0 g, the mixture was stirred at 80 ° C. for 3 hours, and then allowed to stand. After discarding the lower layer, MIBK was distilled and recovered through dehydration and filtration to obtain 470 g of the desired epoxy resin (I). This resin has a binuclear component content of 52% by weight and a bromine content of 4%.
1 wt%, melt viscosity at 150 ° C. was 13.5 poise, and epoxy equivalent was 438 g / eq.

Production Example 2 472 g of an epoxy resin (II) was obtained in the same manner as in Production Example 1 except that the phenol used was changed to 1400 g. This resin had a binuclear component content of 61% by weight, a bromine content of 43% by weight, a melt viscosity at 150 ° C. of 9.8 poise, and an epoxy equivalent of 450 g / eq.

Production Example 3 Epoxy resin (III) (468 g) was obtained in the same manner as in Production Example 1 except that the phenol used was changed to 950 g. This resin had a binuclear component content of 47% by weight, a bromine content of 40% by weight, a melt viscosity at 150 ° C. of 18.2 poise, and an epoxy equivalent of 436 g / eq.

Production Comparative Example 1 462 g of an epoxy resin (IV) was obtained in the same manner as in Production Example 1 except that the phenol used was changed to 500 g. This resin has a binuclear component content of 12% by weight, a bromine content of 35% by weight, a melt viscosity at 150 ° C. of 68 poise,
The epoxy equivalent had a property of 430 g / eq.

Examples 1 to 3 and Comparative Examples 1 to 3 A mixture prepared according to the composition shown in Table 1 was kneaded with a hot roll at 100 ° C. for 8 minutes, and then ground to 1200 to 1400 kg / cm. ^A tablet was prepared at a pressure of ² and was sealed with a transfer molding machine under the conditions of a plunger pressure of 80 kg / cm ² , a mold temperature of 175 ° C., and a molding time of 100 seconds. A flat package was prepared as a test piece for evaluation. Then 175
Post-curing was carried out at 8 ° C. for 8 hours. At that time, a test die was used as an index of fluidity at 175 ° C. 70kg / c
The spiral flow was measured under the conditions of m ² and 120 seconds.

Using this test piece for evaluation, 85 ° C./85%
The water absorption under RH conditions, the glass transition temperature by a viscoelasticity measuring device, and 20 test pieces were left in an atmosphere of 85 ° C. and 85% RH for 72 hours to perform a moisture absorption treatment. Table 1 shows the rate of occurrence of cracks when immersed in a solder bath for 10 seconds.

Here, 153 is a tetrabromobisphenol A type epoxy resin (Dainippon Ink and Chemicals, Inc.)
Product name: EPICLON 153, bromine content 48
% By weight, melt viscosity at 150 ° C. 1.1 poise, epoxy equivalent 401 g / eq), BREN is a brominated phenol novolak resin (trade name BREN-S, manufactured by Nippon Kayaku Co., Ltd.)
34% by weight bromine content, melt viscosity at 150 ° C. 11.6
Poise, epoxy equivalent 283 g / eq). N-665
Is an orthocresol novolak type epoxy resin (trade name: EPICLON N manufactured by Dainippon Ink and Chemicals, Inc.)
-665, epoxy equivalent 208 g / eq, melt viscosity at 150 ° C. 3.0 poise), TD-2131 is a phenol novolak resin (trade name: Phenolite TD-2131, manufactured by Dainippon Ink and Chemicals, Ltd., softening point 80 ° C.) , Hydroxyl equivalent 104 g / eq). The melt viscosity at 150 ° C. and the bromine content in Table 1 were determined by comparing each halogenated epoxy resin with N-
665 in the mixture.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

According to the present invention, an epoxy resin composition exhibiting excellent flame retardancy and having both excellent moisture resistance and fluidity, and excellent flame retardancy and solder crack resistance. Semiconductor sealing material can be provided,

Claims (16)

[Claims] 1. A polyaddition product of an unsaturated aliphatic cyclic hydrocarbon compound and a phenol, which is a reaction product of a compound having a halogen atom in its molecular structure with epihalohydrin, and An epoxy resin composition comprising a halogenated epoxy resin (A) having a core component content of 35% by weight or more and a curing agent (B) as essential components. 2. The halogenated epoxy resin (A) of 150
The composition according to claim 1, which has a melt viscosity at 25 ° C of 25 poise or less. 3. The composition according to claim 1, wherein the epoxy equivalent of the halogenated epoxy resin (A) is in the range of 350 to 500 g / eq. 4. The composition according to claim 1, further comprising another epoxy resin (C) in addition to the halogenated epoxy resin (A) and the curing agent (B). 5. The composition according to claim 4, wherein the content of halogen atoms in the epoxy resin (A) is in the range of 15 to 50% by weight. 6. The composition according to claim 4, wherein the melt viscosity at 150 ° C. of the mixture of the halogenated epoxy resin (A) and the epoxy resin (C) is 3.0 poise or less. 7. The composition according to claim 1, wherein the total halogen atom content in the composition is in the range of 5 to 40% by weight in the organic component. 8. A polyaddition product of an unsaturated aliphatic cyclic hydrocarbon compound and a phenol, which is a reaction product of a compound having a halogen atom in its molecular structure with epihalohydrin, and A semiconductor encapsulating material comprising, as essential components, a halogenated epoxy resin (A) having a core component content of 35% by weight or more, a curing agent (B), and an inorganic filler (D). 9. The halogenated epoxy resin (A) of 150
9. The semiconductor encapsulating material according to claim 8, having a melt viscosity at 25 ° C. of 25 poise or less. 10. The semiconductor encapsulating material according to claim 8, wherein the epoxy equivalent of the halogenated epoxy resin (A) is in the range of 350 to 500 g / eq. 11. The semiconductor encapsulation according to claim 8, 9 or 10, further comprising another epoxy resin (C) in addition to the halogenated epoxy resin (A), the curing agent (B) and the inorganic filler (D). material. 12. The semiconductor encapsulating material according to claim 11, wherein the halogen atom content in the halogenated epoxy resin (A) is in the range of 15 to 50% by weight. 13. The semiconductor encapsulating material according to claim 11, wherein a melt viscosity of the mixture of the halogenated epoxy resin (A) and the epoxy resin (C) at 150 ° C. is 3.0 poise or less. 14. The semiconductor encapsulating material according to claim 8, wherein the total halogen atom content in the semiconductor encapsulating material is in the range of 5 to 40% by weight in the organic component. 15. A filling amount of the inorganic filler (D) is from 70 to
The semiconductor encapsulant according to any one of claims 8 to 14, wherein the amount is in the range of 95% by weight. 16. The semiconductor sealing material according to claim 8, wherein a part of the inorganic filler (D) is spherical silica.